Treatment of hydrocarbons



'- D@ 26, w22. Mmm@ G. F. FoRwoon.

TREATMENT oF HYDRocARa'oNs.

FILEDDEC, 20. 1917,

CoMPIEssm OUTLET ow 0IA HNI' Inl/ITER 0u. rf/mf Comun/.SERS

Cdn/35H5 ture, in fact, it is advisable wPatentedDer:o 26, 1922.,

UNTTED sTaTas GEORGE FREDERICK FORWOOD,

' Maaate vor LoNDoN, ENGLAND, AssrGNoR, BY DIRECT ann MESNE ASSIGNMENTS, T0 ,TI-IE UNITED KINGDOM- OIL COMPANY LIMITED, OF

LONDON, `ENGLAND.

Application filed December 20, 1917. l Serial No. 208,139.

To all whom z'tmay concern.'

Be it known that I, GEORGE FREDERICK FoRWooD, a subject of the King of Great Britain, residing at London, England, have invented certain new and useful Improvements 'in the Treatment of Hydrocarbons (for which I have iiled applications in England December 12, 1916, and December 22, 1916), of which the followingv is a specification.

My invention consists in passing the vapour of coal oil; shale oil; petroleum, or lignite oil mixed with steam or water vapor over hot carbon or a kfnd capable of decomposing steam or water vapor when both are at a heat below a temperature of 600 C., 'so that, the carbonliberates hydrogenI from the steam; and this hydrogen is taken up by the oil hydrogenating it, the object being to obtain an oil or spirit, such as petrol, suitable as a motor fuel and for other uses.

Proposals of this sort have been made before, but to secure success it is necessary (l) that the temperature is not too high, as that destroys the: oil,` (2) that the carbon shall be in such a condition that it will decompose 4the steam or water vapor at a low enough 'temperature not to injure the oil, and

that there must be enough steam or water vaporttoinsure that sufficient is decomposed at the working temperature.

In order that the carbon shall be suitable it must be in a physical condition in which it will decompose steam or watervap or at the temperature used. Thus, if an oil is being treated which requires a temperature of about 500 C., to combine with the hydrogen produced by the decomposition of the steam or water vapor passing over the heated carbon, the carbon must be or water/vapor available. The carbon must be preparedwithout being heated to a high tem erature. Thus, if oil residue, or carbonize 4o il is to' be used it must not be heated much above the'working temperapossible at theworking temas-nearly as perature, 'but to carbonize itl it Vmay be heated beyond this i 1 s c within reasonable limits, though there is no object in so heating it.

Lampblack, soot, wood, cellulose, and lignite charcoal may stand a higher temperat'ure without losing the power of decomposingwater at the ,temperature of working, but again it' is best not to carbonize them at temperatures much higher than those atwhich they are to be used. Different o-rganic bodies may have their carbonaceous residues heated to different temperature without destroying their action on steam or water vapor at temperatures below 600O C. The .kinds of carbon necessary for use according to the present invention may be obtained from any carbonizable body by carbonization thereof at a temperature below 600 C., and primarily a carbon will be selected that is active at acomparatively low temperature for treating oil vapor by deoxidizing steam or water vapor in its presence at temperatures that will not destroy the oil.-

team or Water vapor is used in excess, because the decomposition at low temperatures goes best'in excess.

The temperature of operation on the oil l generally it is be- The'most perfect result is the mere addition of hydrogen tothe oil vapor, without reducing its carbon. This involves c onsumption of the 'solid carbon supphed. The next best result is to add hydrogen, and

to oxidize some of the carbon in the oil vapor at the same time. If carbon is -deposited it means that most of it, if not all, the oxide of carbon formed is also at the expense of the carbon in-the oil vapor. J

The best temperature` and the proportlon of water vapour have tolbe found by trial for each oil; I have found various temperatures between 500 C. and 600 C, suitablev for di'erent oils.

Tt is not always necessary to crack the dierent oils. In may. Cases it is advvantageous merely to add h drogen by this' process. `n important res'i t of my process s thai-it the @Il contains sulphur, most, aad

theoutlet o the scrubberv n at this'l point.

in some cases', all of it is eliminated as sulphuretted hydrogen.

Examples of the treatment of specific oils according to this invention are given as fol` lledwith the selected carbon of comparatively low carbonizino' temperature and the vapors leaving thereto are condensed and treated in the ordinary manner. ducting experiments, I took 140 cubic centimetres of kerosene (boiling point 170 C. to 200o C.) and the carbon employed was prepared from willow Wood carbonized at a low t'emperature,'i. e. at about 400O C.) the retort bei heated to a tem erature of labout 57 00u-. vThe proportion o steamused was equivalent.to4.7 volumes of Water to one volume' of oil. The(7 time occu ed inpassing. the 140 cc.y of atomized oil t rough vthe' retort filled withr heated carbon was sixty five minutes. After ,passing pours'were led through a Water cooled condenser and the'condensed portion was c ol-v lected Vin a suitable receiver. The uncondensfed uapours then passed upwards through 'a scrubber filled lwith scrubbing material suc-h as coke or brokenbrick, While heavy oil such creosote oill passed through the scrubber in the lopposite direction to the vapours.

Before the creosote oil was used for scrubbmg purposesall the fractions-below 2400 C. were first removed. 'ln the receiver and.

scrubber about 48 per cent of the original Volume of the kerosene Was collected as a. light oil vof a boiling point between 49 and 170 C. About -40' per cent of the original volume yof -the'kerosene remained unaltered and was available for further treatment, the balance of 12 per cent `was converted' into ,gas suitable for heating the retort or for steam. raisin' A sample of gas collected at I gave Ithe followingresults on analysis-j` arbon dioxide,1'oxygen ydrocarbons(methan e etc.) :7%.y Hydrogen=%.4 'l

Nitrogen-5% by Volume.

i froinfthe oil fand that producedby the derl composition of the steam used.

thro-ugh the retort the va.

v and carbon mon' 66- ox1detogether=28% by volumemetisse, r.

(b) For hydrogenation of light oils or spirits which already have been cracked, the treatment is similar tol that to which heavier retort is about 500 C. A

N otaHVVhere heat is `employed in the production of hydrogen through the decomposition of steam by carbon, it is extremely diflicult to hydrogenate the unsaturated bodies Without some slight loss of oildue to crack-A with 1n a similar manner to that described under (a).

ln the receiver and scrubber about 95 per cent of the original volume of the cracked spirit was collected. The remaining five percent `Was converted into gas suitable oils are subjected except that the heat of the` through the retortthe vapours were dealt In. con- 1 for heating ,the retort or for steam raising.

A sample of gas'collected at the outlet of the serubbergave the followingresultaon analysis Carbon oxide together::25% by volume. 'l Hydrocaibons (methane etc.):4%. Hydrogen:64%. Nitrogen=6% by volume. I This gas is a'mixture of the gas produced from `the spirit and that produced by the decomposition ofthe steam used.'l

The hydrogenated spirit was compared .with the spirit before hydrogenation by means of agitation with a saturated aqueous olution of bromine; the biomine is absorbed J11d decolouriz'edL by the unsaturated bod# /ies present in the spirit and the brominatng was taken as complete when the last single drop'of bromine solution remained a/pale yellow colour after addition toand vagitation with the spirit. It was found that the spirit before hydrogenation required .three times as much biof y contained 66?; per cent'- less of the unsatuf.

rated bodies than inal irit. v .(0) For the pounds only.

was 1contained inthe .origproduction of hydrogen through .the .de- .composition o'f steamaby carbon, it is not n-Witho'utl .at the same time hydrogenatlig' the I unsaturated bodies; v233 cubic centif dioxide, oxygen and carbon monreinxval1 of 1 sulphur i coin-v N0a. where heafis empioyedfin' the practicable to hydgrogenate the su1phur This gas vis a mixture ofthe gas prc'iduceo't I n 'metresofalight spirit distilled froma shale 1.80

oil were passed with steam through a retort filledwith carbon heated to a temperature of about 530O C rllhe proportion of steam used was equivalent to 2g vo-lumes of water to one volume of spirit. The time occupied in passing the 23.3 c. c. of spirit through the retort filled with heated carbon was 60 minutes.

In passing through sulphur contained in the heated carbon the the spirit was hydrogenated by the hydrogen produced by the decomposition of the steam, sulphuretted hydrogen being thereby formed, which escaped together with the other gases carbon dioxide, hydrogen etc.) at the outlet of the retort. .v The condensed spirit together with that scrubbed out of the gases by the scrubber oil (heavy creosote) were collected and washed with a dilute solution of caustic soda in order to remove any sulphuretted hydrogen, this was followed by a washing with water toremove all traces of soda.

The sulphur content in the finished spirit was found to be equal to 1.8 per cent by weight, whereas that in the original spirit was found to be equal to 4.9 per cent by weight, hence there is a reduction of sulphur in the hydrogenated spirit equal to 3.1 per cent by weight or equivalent to a reduction of 63 per cent of the original weight of the sulphur.

The foregoing process is not in the least limited to any particular apparatus, but for the purpose of demonstration the drawing illustratesa sectional elevation of an apparatus suitable for carrying out the improved process or method.

Referring to this drawing: A is a tank for containing the oil to be treated and has a pipe B connected thereto and a suitable air compressor, not shown, and whereby aircompression is passed to the tank to act upon the surface of the oil in the latter'. A pipe C extends downwardly into and near the bottom of the tank A and leads vaway from` the top of the tank and connects withy an 'injector nozzle D, ad;- jacent to the attachment to the nozzle of a steam pipe E leading from a suitable source of steam supply for mixing steam with the oil after it passes from the said injector D.

etween the walls G of a furnace or heater a retort F is supported to an angle and has its lower end connected to a continuation of the pipe C on the opposite side of the injector or nozzle D and in advance of the connecti retort 1s a perforated iron stopplate H adapted to support charcoal I in the retort at the lower end of the latter. From the upper end of the retort a pipe\J. extends and is connected by abranch pipe K and a dip pipe L to a hydraulic main M for passing the products of combustion from leading from on ofthe steam pipe E. Within the ugh the se the gases passing from one other through the Vmed usual and are condense the condensed gases and vap 1n the receivers S from w by a pipe T to an yoil ta va ber V; This scrubber V brick, coke or boards heavy oil is supplied to suitable pump by the pipe W and over the broken coke or X, and after brick or coke, way of the outl pors passing by way of pipe U passing through t Hows to a storage tank by et pipe Y. Any oil from the d main and causing the hrough the liquid in the aving an outlet N for oil `The gases and vapors, after al in theliydraulic by a pipe P intoa and may be colatmospherically, condenser to anium of pipes R as d, and the oil from ors is deposited l hich it is taken nk, the uncondensed to a scrub'- is filled with broken laid crosswise and the scrubber from a is sprayed he sprayer he broken brick by t uncondensed gases and vapors passed to the scrubber V from the pi the receiver Z an of the seal pipe away form the pe U is collected in d passes to a tank by way a, the finished scrubber V by It will be understood that be inclined inwany manne gas passing the pipe 5. the retort F may r to render it effective in the performance of its function and any type of con andin some cases the pensed with and a rot place thereof.

`What I do claim as desire to secure by l. The herein d ing unsaturated h genate the same, c oil to pressure to escrib atom mixing the atomized oil \ing the mixed atomize posed solely of a light rcoal heated at Cto decompose the perature, and conveyors formed to a pluraleparate the vapors and fthrough a mass com porous form of cha perature below 6000 steam below this tem ing the gases and vap ity -of condensers to s oil from the-condensed 2.' The herein describ ing hydrocarbon oils same, which consists in pressure to atomize it ing the atomized oil wit mixed atomized oil an mass of light porous c temperature below 600o Water vapors below this rating the vapors and densed gases and vapo plying sprayed heavy oi densers may be used, scrubber may be disary washer used in my invention,y and Letters Patent, is zed process of treatydrocarbon oils 'to hydr onsisting in subjecting the ize it and. instantly with steam, passd oil and steam a tem- `gases and vapors.

ed vprocess of treattor4 hydrogenate, the subjecting the oil to and instantly mixh steam, passing the d steam through a arcoal heated at a C to decompose the temperature, sepa- Oil from the conrs, and finally supl to t gases and remaining vapors.

3. The herein describe genatingJ oils', consistin d process of hydrog in subjecting the he uncondensed oil to pressulfeto atomize it and' instantly mixing the atomized oil with steam, passing the mlxed atomized oil and steam solely Athroughl a mass of charcoal heated to a temperatre below 600 C. to decompose the steam and with 'the resultant hydrogen in its nascent or atomic condition at the moment of its liberation from the steam' effecting a ('ombination with the unsaturated bodies in the craoked oil and converting tliern 10 -into saturated bodies. 

